CN101389674A - Novel melamine-formaldehyde condensates with thermoplastic properties - Google Patents
Novel melamine-formaldehyde condensates with thermoplastic properties Download PDFInfo
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- CN101389674A CN101389674A CNA2007800062472A CN200780006247A CN101389674A CN 101389674 A CN101389674 A CN 101389674A CN A2007800062472 A CNA2007800062472 A CN A2007800062472A CN 200780006247 A CN200780006247 A CN 200780006247A CN 101389674 A CN101389674 A CN 101389674A
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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Abstract
The invention relates to melamine-formaldehyde condensates with thermoplastic properties that can be produced from formaldehyde and melamine derivatives, wherein at least one of the melamine derivatives organic radicals R have been used to substitute at least four of the total of six hydrogen atoms of the three melamine amino groups, and wherein the organic radicals R are mutually identical or different. The invention also relates to a process for production of the melamine-formaldehyde condensates, use thereof, and an analytical method for determining the constitution of the melamine-formaldehyde condensates.
Description
The present invention relates to according to the thermoplastic novel melamine-formaldehyde condensates of having of claim 1, according to the method for the described condensate of melamine and formaldehyde of preparation of claim 14, according to the purposes of the described condensate of melamine and formaldehyde of claim 17 and according to the method for the described condensate of melamine and formaldehyde of analysis of claim 18.
Condensate of melamine and formaldehyde mainly is used as the tackiness agent of glued board, laminating material in timber industry, the linking agent of coating and the adhesives of moulded product.These conventional resins are highly cross-linked, are rigidity hard thermoset plastic materials therefore.Crosslinkedly also can carry out at low temperatures usually, make uncrosslinked material not to be melted, but therefore not have the thermoplastic processibility.
Past, but select different solutions to improve for example thermoplastic processibility of terpolycyantoamino-formaldehyde resin of aminoplastics.
A kind of method is that the melamine resin of etherificate is carried out ether exchange reaction (WO03/106558).Wherein, at first make trimeric cyanamide aldehyde precondensate and low mass molecule alcohol etherificate, carry out ether exchange reaction with high molecular alcohol subsequently.Zhi Bei cross-linked resin has good melting characteristic like this, that is to say, has enough big processing space between its melt temperature and beginning solidified temperature.
The shortcoming of the melamine resin of known etherificate is: they are strong crosslinked, so viscosity is high relatively, even also are like this in melt.When introducing filler, viscosity further raises, make filler almost can not be in resin uniform distribution.In addition, high viscosity makes that the flowability of resin melt in machining tool is poor.
WO 2005/010097 has described the method for another kind of raising melamine resin moulding material flexibility.At this, crosslinked melamine resin ether mixes with crosslinked thermoplastics.Crosslinked thermoplastics, for example ethylene-vinyl acetate copolymer or ethylene-acrylate copolymer play the effect of lubricant, therefore improve the flow of molding material performance.Its shortcoming is, makes the mechanical property variation of moulding material owing to add thermoplastics.
The another kind of method that changes melamine resin character is for example to use the melamine derivative of modification to carry out condensation reaction.Therefore, with the alkylating melamine derivative of N-prepare polymer product and with the condenses of formaldehyde be known.
N-alkyl melamine formaldehyde composition as the coating system linking agent has been described in U. S. application 2005/0282994 and 2005/0014869.Dialkyl group trimeric cyanamide and trialkyl trimeric cyanamide or their mixture have especially been described and with its carbamate or comprise the crosslinked of compound bearing active hydrogen.
In United States Patent (USP) 3056755 and 2980637, described the condenses of dialkyl group trimeric cyanamide and trialkyl trimeric cyanamide and they and formaldehyde and also had alcohol in some cases as the baking finish component.Yet described resin always has only a kind of component, and it is generally used for the crosslinked of Synolac.The purposes of this condenses is limited to the coating system of trimeric cyanamide product as linking agent.Described condenses is suitable for forming cross-linked polymer, and its melt can not be processed or the non-constant of processibility usually.In addition, the thermoplasticity of condensate of melamine and formaldehyde is not made report in the above-mentioned document yet.
But the purpose of this invention is to provide have good thermoplastic processibility, the novel melamine-formaldehyde condensates of good postforming and good mechanical properties.
Above-mentioned purpose realizes by the condensate of melamine and formaldehyde that the feature with claim 1 is provided.
Has thermoplastic condensate of melamine and formaldehyde by formaldehyde and melamine derivative preparation according to of the present invention, wherein at least a melamine derivative, at least four are replaced by organic group R in six hydrogen atoms altogether of three amino of trimeric cyanamide, and described organic group R is same to each other or different to each other.
Therefore, the amino of trimeric cyanamide exists with the form that N-replaces.So melamine derivative used according to the invention has only two free hydrogen atoms that can carry out other chemical reaction on the amino of trimeric cyanamide.
Described free hydrogen atom preferably is present on two secondary amino groups.This is because the chemical reactivity of primary amine and secondary amine is different, replaces and always preferably at first takes place on primary amino, just takes place on secondary amino group subsequently.Therefore, melamine derivative used according to the invention preferably has two secondary amino groups and uncle's amino.
Therefore, when melamine derivative used according to the invention and formaldehyde reaction, each melamine rings only forms two methylols, preferably forms on two different secondary amino groups.This causes further being preferably formed linear oligomer and polymkeric substance in the condensation course.
Under proper temperature, the linear chain molecule can slide over each other, thereby makes resin also fusible and can carry out thermoplasticity processing under low relatively temperature.Therefore, condenses according to the present invention has extraordinary flowing property and can be distributed in the shaping jig admirably.
When in six amino hydrogen atoms of the used melamine derivative when 100% four are substituted, obtain pure line style condensate of melamine and formaldehyde.When this melamine derivative and formaldehyde reaction, the polymkeric substance that so obtains is forced to accept linear structure.
Described condensate of melamine and formaldehyde advantageously comprises 10 to 99% melamine derivatives, in described melamine derivative in six hydrogen atoms altogether of three of trimeric cyanamide amino at least four replaced by organic group R.
Except above-mentioned quaternary at least melamine derivative, other component also can be present in the described condensate of melamine and formaldehyde.Therefore, advantageously use unsubstituted trimeric cyanamide or single the replacement to hexabasic melamine derivative or its mixture.Therefore, the substitution value of the melamine derivative that uses in the mixture is variable.Under the different situation of substitution value, can use identical organic group R and different organic group R.
Therefore, can prepare condensate of melamine and formaldehyde with different ratios linear structure.When in six amino hydrogen atoms of the used melamine derivative when 10 to 99% four are substituted, six amino hydrogen atoms altogether of then remaining 90% to 1% used melamine derivative can have zero to six to be replaced by organic group, perhaps can use the mixture of any hope of these melamine derivatives.
Advantageously, described condensate of melamine and formaldehyde also comprises 90% to 1% acetylguanamine, benzo guanamine, replacement or changes amino acetylguanamine or benzo guanamine, phenol or its mixture of wishing arbitrarily except the melamine derivative that comprises described at least four N-replacement.
Advantageously, with C
1-C
20Alkyl, C
5-C
30Cycloalkyl, C
6-C
24Aryl, C
7-C
30Aralkyl, hydroxyl-C
2-C
10Alkyl, hydroxyl-C
2-C
4Alkyl-(oxa--C
2-C
4Alkyl)
n(wherein n is 1 to 5) and/or amino-C
2-C
12Alkyl is as the organic group R that is suitable for deriving or N-replaces.
Preferred ethyl, propyl group, sec.-propyl or phenmethyl, especially preferable methyl.An advantage using methyl is that they are easy to introduce by multiple methylating reagent.Another advantage is, methyl is very little, and is therefore faint to the influence of trimeric cyanamide structure, and the property that has kept trimeric cyanamide thus as much as possible is therefore faint to the influence of trimeric cyanamide structure, kept the character of trimeric cyanamide thus as much as possible.
Condensate of melamine and formaldehyde advantageously has the part linear structure, but preferred linear structure fully.
Generally speaking, by targetedly the amino of trimeric cyanamide being carried out derivatize or N-replaces, preparation has the novel material of interested new property before the preparation condensate of melamine and formaldehyde.Have the mixture of the melamine derivative of different degree of substitution by changing N-substitution value or use, and, can in wide region, change these character by mixing with the trimeric cyanamide of underivatized.
Derivatize or N-replacement by amino can make the solvability of pyrrolotriazine derivatives improve.Therefore allow under mild conditions, to prepare resin, at room temperature also can react in some cases thus with formaldehyde.In addition, because all melamine derivatives have just existed with solubilized form rather than just become solution by reaction when the reaction beginning, obtain basically resin uniformly thus.Therefore by selective reaction condition and reaction times, can set and be preferably formed monomer, dimer, tripolymer or oligopolymer.Therefore, obviously can obtain narrow molar mass distribution.Yet, also can extensively change wide molar mass distribution by the composition that comprises different melamine derivatives.
In addition, advantageously, because the solvability of the trimeric cyanamide of derivatize improves, the ratio of can also be when the preparation resin amount of formaldehyde being reduced to melamine derivative and formaldehyde is 1:1.Yet, can realize the crosslinked of resin by elevated temperature or interpolation curing catalysts.Can also prepare the component that formaldehyde volatile matter and VOC volatile matter all reduce thus.
Advantageously, be 70 to 130 ℃ according to the melting range of condensate of melamine and formaldehyde of the present invention, melt viscosity is 0.1 to 100Pa.s.
The feature of described condenses is that also in 70 to 130 ℃ temperature range, most of linear condensation thing does not take place crosslinked.Most of linear condensation thing only temperature surpass 130 ℃ or add curing catalysts after just take place crosslinked.
The methylol of condensate of melamine and formaldehyde is preferably partly or entirely by etherificate, and the alcohol that preferably is used for etherificate is the monoalky lether of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, hexalin, phenol, phenylcarbinol, ethylene glycol or monoalky lether or its mixture of propylene glycol.
Purpose of the present invention is also by realizing according to the method for preparing condensate of melamine and formaldehyde of claim 17 with according to the purposes of the condensate of melamine and formaldehyde of claim 21 and 22.
According to the present invention, described condensate of melamine and formaldehyde prepares according to following method, and being reflected in solvent, the preferably water of following material and formaldehyde carried out, and described material is 1:1 to 1:6 with the ratio of formaldehyde, preferred 1:1 to 1:3,
A) melamine derivative, in described melamine derivative in six hydrogen atoms altogether of three of trimeric cyanamide amino at least four replaced by organic group R, and/or
B) according to a) melamine derivative and the mixture that meets the melamine derivative of following condition, three amino does not have hydrogen atom and/or has one to six hydrogen atom to be replaced by organic group in six hydrogen atoms altogether in described melamine derivative, and/or
C) according to a) melamine derivative and acetylguanamine, benzo guanamine, replacement or change the mixture of amino acetylguanamine, guanamines and/or phenol.
Described reaction is advantageously carried out in alkaline medium, but also can carry out in neutrality or acidic medium.
The melamine derivative of Shi Yonging is with C in the method according to the invention
1-C
20Alkyl, C
5-C
30Cycloalkyl, C
6-C
24Aryl or C
7-C
30Aralkyl, hydroxyl-C
2-C
10Alkyl or hydroxyl-C
2-C
4Alkyl-(oxa--C
2-C
4Alkyl)
n(wherein n is 1 to 5) and/or amino-C
2-C
12Alkyl is as organic group, especially methyl, ethyl, propyl group, sec.-propyl or phenmethyl.
Described condensate of melamine and formaldehyde is advantageously used alcohol, the monoalky lether of particular methanol, ethanol, propyl alcohol, Virahol, butanols, hexalin, phenol, phenylcarbinol, ethylene glycol or the monoalky lether of propylene glycol or its mixture etherificate under the acidic catalyst condition.
Condensate of melamine and formaldehyde according to the present invention uses as the tackiness agent of laminating material.Described condenses also has postforming (postforming) character under the situation of not carrying out the methylol etherificate.Obtained because both can in solution, obtain also to can be used as the exsiccant powder, so wet impregnation and dry method dipping are all feasible according to condensate of melamine and formaldehyde of the present invention.
In addition, can be according to condensate of melamine and formaldehyde of the present invention as the tackiness agent of the matrix material that comprises natural fiber, glass fibre, woodwork and other filler and additive.Described matrix material can comprise for example timber, natural fiber, glass fibre, organic or inorganic filler or synthon (for example polymeric amide, polyester).
Condensate of melamine and formaldehyde according to the present invention is suitable for that all conventional working methods are for example injection-molded, compression molding, extrude etc.
Can also be according to condensate of melamine and formaldehyde of the present invention as the component of coating system.
Purpose of the present invention also realizes by the method for assay determination according to condensate of melamine and formaldehyde of the present invention.
Structure is measured in combination by different analytical procedures.In addition, the monitor optical spectral property is with the variation of polymkeric substance degree change.Know that these data quantitatively are important to the accurate of single material in the complicated resin compound.
The separation of resin Composition realizes by high pressure liquid chromatography (HPLC) and gel permeation chromatography (GPC).Collect HPLC and GPC fraction,, and result and laser defusing measure result and the external calibration that obtained by the polymkeric substance standard model compared by mass spectroscopy.Analytical procedure comprises HPLC-mass spectrum (MS), ESI-ion trap-MS and MALDI-TOF-MS.
In addition, utilize pyrolysis gas chromatography (Pyro-GC) (GC)-(MS) test sample.
The sign of resin compound is also carried out with the coupling of the ion trap mass spectrometer that can carry out the MSn test by HPLC and PDA detector.
By adopting these methods, can determine the single material in the mixture without doubt.When compound crosslink, these materials will be more and more soluble in the solvent that is suitable for the HPLC/MS measurement.Therefore, utilize GPC system separation resin with IR, UV and light scattering detector and the fraction of collecting, so that determine molar mass accurately by mass spectrometric detection.
Completely crued system is no longer solvable, therefore can not pass through liquid chromatographic detection again.So, utilize analysis pyrolysis and thermal induction hydrolysis and methylate (THM) in the GC/MS system, to characterize.Utilize this technology not only can measure resin Composition but also can measure filler and additive.
Illustrate in greater detail the present invention below with reference to Fig. 1 to 3 and several embodiment.Wherein:
Fig. 1 shows according to the preferred embodiments of the invention production of melamine formaldehyde condensation products.
Fig. 2 A shows the ESI-MS spectrogram of still uncured condensate of melamine and formaldehyde.
Fig. 2 B shows the ESI-MS spectrogram of solidified condensate of melamine and formaldehyde.
Fig. 3 A shows the chromatogram by GPC and MALLS subsequently and RI detection separation of melamine aldehyde products sample.
Fig. 3 B shows the chromatogram by HPLC and MS subsequently and UV detection separation of melamine aldehyde products sample.
Fig. 4 shows the chromatogram by high pressure liquid chromatography (HPLC) separation of melamine aldehyde products sample.
Fig. 5 shows the chromatogram and the mass spectrum (MS) that is used to measure selected fraction molar mass by gel permeation chromatography (GPC) separation of melamine aldehyde products sample.
Fig. 6 shows the pyrogram that pyrolysis GC/MS analyzes.
Embodiment 1: as 2 of methylated melamine derivative, and the preparation of the two methyl of 4--6-dimethyl trimeric cyanamide
Reaction is stirred under 0 to-5 ℃ temperature of reaction in acetone by cyanuryl chloride (1mol) and 2mol methylamine (40%) and is carried out.Add NaOH (2mol) and heat afterwards, reach about 40 to 45 ℃ to temperature.Leach product after about 2 hours of reaction times.Product is stirred in containing the water of excessive dimethylamine, add NaOH simultaneously, and about 2 hours of reflux.With postcooling, filtration and drying.The fusing point Fp of products therefrom is 86 to 87 ℃.
The preparation of 2: the first condensate of melamine and formaldehyde of embodiment
React during with 1mol formaldehyde (be as concentration 37% formalin solution) down at 40 ℃ according to the 1mol methylated melamine of embodiment 1 at pH8.During entire reaction, all obtain suspension, but its denseness considerable change.Finish reaction, filtration product and vacuum-drying after 60 minutes.Obtain fusing point about 120 ℃ and molar mass and be 300 to 400 powder.Product mainly is made up of dimer and tripolymer.Being solidificated under intensification and the acidic catalyst condition of resin carried out.
Fig. 1 shows the route of synthesis, structure of gained condenses and the structural profile of cured resin.
The polymerization that takes place in solidification process by ESI-MS as seen.
Fig. 2 A shows the ESI-MS spectrogram of the still uncured condensate of melamine and formaldehyde of trimethylammonium trimeric cyanamide and tetramethyl-trimeric cyanamide.In 169 to 259Da monomer scope, can detect average substitution degree and be 1 methylolation trimeric cyanamide unit.Comprise three kinds of dissimilar dimers in 349 to 469Da scopes: pregnancy base class (349Da), seven methyl classes (363Da) and prestox class (377Da).The most normal appearance is the hexamethyl dimer (379Da, 409Da) that contains one or two methylol.
Fig. 2 b shows the ESI-MS by formic acid identical condenses after 140 ℃ of following completely solidified.The peak of normal appearance is at about 700Da place and can belong to the tetramer.Extra best best can detect above the 2000Da place.
The separation of resin sample utilizes GPC and follow-up MALLS and RI to detect (Fig. 3 A) monitoring, and utilizes HPLC and follow-up MS and UV to detect (Fig. 3 B) monitoring.Utilize HPLC-MS, can detect the oligopolymer better and separate than GPC.Because substance classes is various, so also can not thoroughly be separated into one isomer.
Fig. 4 shows that UV absorbs the dependency of the maximum value and the polymerization degree.Fig. 4 demonstration utilizes the analysis and characterization of HPLC separation to condenses.To in HPLC, isolate its each component from the resin sample of embodiment 1, and utilize ion trap-MS, ESI-MS and MALDI-TOF-MS to measure the molar mass of each component with the PDA detector.Subsequently, can determine the structure (see figure 1) of each material thus.Form by the more senior homologue of about 55% dimer (n=0), about 35% tripolymer (n=1) and about 10% (n〉1) from the resin of embodiment 1.
Fig. 5 demonstration utilizes the analysis and characterization of GPC/MS to condenses.Utilize RI, UV in the GPC system, to separate from the resin sample of embodiment 1, measure fraction and utilize MS to measure its molar mass with light scattering detector.Therefore can determine the composition of sample equally.
Therefore during completely solidified, the polymkeric substance that obtains is no longer solvable in organic solvent, can not utilize conventional H PLC, GPC or based on the MS technology of solvent.In this case, proved that pyrolysis GC/MS is useful analytical procedure.
Fig. 6 shows the pyrolysis GC/MS spectrogram of solidified tetramethyl-melamine resin.The pyrolytic primary product is from the bond rupture of methylene bridge.
The preparation of 3: the second condensate of melamine and formaldehyde of embodiment
In 90ml water, add 6g tetramethyl-trimeric cyanamide and 24g trimethylammonium trimeric cyanamide, and with mixture heating up to 70 ℃.The formaldehyde of corresponding 1:1 subsequently: triazine is than adding formalin solution (14.3g).The pH value of reaction mixture is 8.2.Described mixture kept 30 minutes down at 70 ℃, cooled off and evaporated on rotatory evaporator.Obtain the resin of white solid form.Described resin is 80 to 100 ℃ of fusings, and molar mass is 300 to 400.By being heated to 140 ℃ of (can add acid) curable described resins, molar mass increases to obviously and surpasses 2000.
The preparation of 4: the three condensate of melamine and formaldehyde of embodiment
In 80ml water, add 10g trimeric cyanamide and 2.5g tetramethyl-trimeric cyanamide and be heated to 80 ℃.Add the formaldehyde of 6g subsequently, and kept 15 minutes down at 70 ℃ as formalin solution.Evaporate with postcooling and on rotatory evaporator.Obtain the resin of white solid form.Described resin is 120 ℃ to 125 ℃ fusings.Molar mass is about 350.
The preparation of 5: the four condensate of melamine and formaldehyde of embodiment
In 100ml water, add the mixture (18% tetramethyl-trimeric cyanamide, 30% trimethylammonium trimeric cyanamide, 24% dimethyl trimeric cyanamide, 15% monomethyl trimeric cyanamide, 13% trimeric cyanamide) of 15g trimeric cyanamide and methylated melamine and be heated to 90 ℃.Add the formaldehyde of 10g subsequently as formalin solution.Mixture is descended maintenance 30 minutes, cools off and evaporates on rotatory evaporator at 90 ℃.Obtain the resin of white solid form.Described resin is 90 to 110 ℃ of fusings.Molar mass is 400 to 500.
Embodiment 6: prepare first laminating material with condensate of melamine and formaldehyde
On the Cavitec device with 150 to 250% from the polymkeric substance spreading decorative paper of embodiment 2 and fixing in the IR field.Subsequently with described paper in extruding 5 minutes under 160 to 190 ℃ and 80 to 110 bar pressures on the laminating machine.Sample has slick mat surface.The result of acid test is than pure MF resin difference one-level.
In the deformation test according to EN438 method A, the bending radius of the laminating material of 0.7mm can reach 3 to 4mm.
Embodiment 7: prepare second laminating material with condensate of melamine and formaldehyde
On the Cavitec device with 150 to 250% 90% from the mixture spreading decorative paper of the polymkeric substance of embodiment 2 and 10%Lamelite 139 (from the MF resin of AMI) and fixing in the IR field.Subsequently with described paper in extruding 5 minutes under 160 to 190 ℃ and 80 to 110 bar pressures on the laminating machine.Sample has slick mat surface.The result of acid test is suitable with pure Lamelite139.
In the deformation test according to EN 438 method A, the bending radius of the laminating material of 0.7mm can reach 3 equally to 4mm.
Embodiment 8: prepare moulded product with condensate of melamine and formaldehyde
On the Cavitec device, with 35% resin spreading flax fiber supatex fabric from embodiment 2.Subsequently that described polymkeric substance is fixing in the IR field.Subsequently with these prepregs (prepreg) 190 ℃ and 120 the crust under the extruding 3 minutes.Take out sample after being cooled to 70 ℃ again.
The mechanical property of the sample mechanical property with the sample made from unsubstituted melamine resin basically is suitable.
Embodiment 9: prepare matrix material with condensate of melamine and formaldehyde
A) 50g is being added 0.5g NH according to the resin of embodiment 2 and the mixture of 50g timber
4Under 150 ℃ and 80 bar pressures, be squeezed into plate under the situation of Cl.The Young's modulus of this plate in pliability test is 2295MPa.
B) 15g is being added 0.15gNH according to the resin of embodiment 2 and the mixture of 50g timber
4Under 150 ℃ and 80 bar pressures, be squeezed into plate under the situation of Cl.The Young's modulus of this plate in pliability test is 3116MPa.
C) 15g is being added 0.15gNH according to the resin of embodiment 3 and the cellulosic mixture of 50g
4Under 150 ℃ and 80 bar pressures, be squeezed into plate under the situation of Cl.The Young's modulus of this plate in pliability test is 4258MPa.
Be used for comparison, the Young's modulus of the standard shaving board of Egger (8mm is thick, 95% timber) is 2282MPa.
The preparation of 10: the five condensate of melamine and formaldehyde of embodiment
With 693.6g N, N '-dimethyl trimeric cyanamide, 91.8g water and 584.1g concentration are that 37% formalin is heated to 60 ℃ together, until obtaining settled solution.Be cooled to room temperature subsequently rapidly.
With 756.9g N, N ', N "-trimethylammonium trimeric cyanamide, 135g water and 584.1g concentration are that 37% formalin at room temperature stirs together, until be settled out formed melamine methylol from solution.Subsequently this mixture and said mixture and other 350g are merged according to the melamine derivative of embodiment 1, and heated 15 minutes to 60 ℃.Obtain settled solution thus.After lyophilize, obtain the resin of white solid form.
Embodiment 11: use condensate of melamine and formaldehyde and prepare matrix material
On the Cavitec device with 35% resin spreading flax fiber supatex fabric from embodiment 10.Subsequently that described polymkeric substance is fixing in the IR field.Subsequently with this prepreg 160 ℃ and 250 the crust under the extruding 4 minutes.Take out sample after being cooled to 70 ℃ again.
The mechanical property of matrix material can see the following form.
| Tensile modulus MPa | Tensile strength MPa | Modulus in flexure MPa | Flexural strength MPa | Impact toughness kJ/m 2 |
| 9320 | 77.2 | 8311 | 131.7 | 20.5 |
According to VDA 275 (formaldehyde) and VDA 277 (VOC-volatile organic content), the component volatilization amount is respectively 29.6ppm and 18.5ppm.
The component volatilization amount of the comparative composite of being made by Lamelite 139 (terpolycyantoamino-formaldehyde resin) is respectively 45.0ppm and 77.0ppm.
Claims (23)
1. one kind has thermoplastic condensate of melamine and formaldehyde, it can be by the prepared in reaction of formaldehyde and melamine derivative, wherein at least a described melamine derivative, at least four are replaced by organic group R in six hydrogen atoms altogether of three amino of trimeric cyanamide, and described organic group R is same to each other or different to each other.
2. according to the condensate of melamine and formaldehyde of claim 1, it is characterized in that: described condenses comprises 10 to 99% melamine derivatives, in described melamine derivative in six hydrogen atoms altogether of three of trimeric cyanamide amino at least four replaced by organic group R.
3. according to the condensate of melamine and formaldehyde of claim 1 or 2, it is characterized in that: described condenses comprises 90 to 1% melamine derivatives or its mixture, and three amino does not have hydrogen atom or have one to six hydrogen atom to be replaced by organic group R in six hydrogen atoms altogether in described melamine derivative.
4. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: described condenses comprises 90 to 1% acetylguanamines, benzo guanamine, replacement or changes amino acetylguanamine or benzo guanamine, phenol or its mixture of wishing arbitrarily.
5. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: at least one organic group R is C
1-C
20Alkyl, C
5-C
30Cycloalkyl, C
6-C
24Aryl and/or C
7-C
30Aralkyl.
6. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: at least one organic group R is ethyl, propyl group, sec.-propyl and/or phenmethyl.
7. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: at least one organic group is a methyl.
8. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: at least one organic group is hydroxyl-C
2-C
10Alkyl, hydroxyl-C
2-C
4Alkyl-(oxa--C
2-C
4Alkyl)
n, wherein n is 1 to 5, and/or amino-C
2-C
12Alkyl.
9. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: described condenses is the part linear structure.
10. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: described condenses is complete linear structure.
11. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: the melting range of described condenses is 70 to 130 ℃.
12., it is characterized in that: in 70 to 130 ℃ temperature range, do not take place crosslinked between most of linear condensation thing according at least one condensate of melamine and formaldehyde in the aforementioned claim.
13. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: the melt viscosity of described condenses is 0.1 to 100Pa.s.
14., it is characterized in that according at least one condensate of melamine and formaldehyde in the aforementioned claim: most of linear condensation thing temperature surpass 130 ℃ or add curing catalysts after take place crosslinked.
15. according at least one condensate of melamine and formaldehyde in the aforementioned claim, it is characterized in that: methylol exists with part or all of etherificate form.
16. the condensate of melamine and formaldehyde according to claim 15 is characterized in that: described methylol is to exist by the monoalky lether of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, hexalin, phenol, phenylcarbinol, ethylene glycol or the monoalky lether of propylene glycol or the form of its mixture etherificate.
17. one kind prepares according at least one the method for condensate of melamine and formaldehyde in the claim 1～16, it is characterized in that:
Following material and formaldehyde are reacted in solvent, preferably water, and described material is 1:1 to 1:6 with the ratio of formaldehyde, preferred 1:1 to 1:3,
A) melamine derivative, in described melamine derivative in six hydrogen atoms altogether of three of trimeric cyanamide amino at least four replaced by organic group R, and/or
B) according to a) melamine derivative and the mixture that meets the melamine derivative of following condition, three amino does not have hydrogen atom or has one to six hydrogen atom to be replaced by organic group in six hydrogen atoms altogether in described melamine derivative, and/or
C) according to a) melamine derivative and acetylguanamine, benzo guanamine, replacement or change the mixture of amino acetylguanamine, guanamines and/or phenol.
18. the method according to claim 17 is characterized in that: described being reflected in the alkaline medium carried out.
19. the method according to claim 17 or 18 is characterized in that: at least one organic group R is C
1-C
20Alkyl, C
5-C
30Cycloalkyl, C
6-C
24Aryl or C
7-C
30Aralkyl, hydroxyl-C
2-C
10Alkyl, hydroxyl-C
2-C
4Alkyl-(oxa--C
2-C
4Alkyl)
n, wherein n is 1 to 5, and/or amino-C
2-C
12Alkyl, especially methyl, ethyl, propyl group, sec.-propyl or phenmethyl.
20., it is characterized in that according at least one method in the claim 17～19: described condensate of melamine and formaldehyde under the acidic catalyst condition with the monoalky lether or the mixture etherificate of the monoalky lether or the propylene glycol of pure particular methanol, ethanol, propyl alcohol, Virahol, butanols, hexalin, phenol, phenylcarbinol, ethylene glycol.
21. according to each condensate of melamine and formaldehyde in the claim 1～16 as the purposes of tackiness agent in laminating material and/or the matrix material.
22. according to each condensate of melamine and formaldehyde in the claim 1～16 as the purposes of coating composition.
23. method that is used for assay determination according to the condensate of melamine and formaldehyde of at least one of claim 1～16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06075451 | 2006-02-23 | ||
| EP06075451.2 | 2006-02-23 | ||
| DE102006027760.0 | 2006-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101389674A true CN101389674A (en) | 2009-03-18 |
Family
ID=38319966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800062472A Pending CN101389674A (en) | 2006-02-23 | 2007-02-22 | Novel melamine-formaldehyde condensates with thermoplastic properties |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US8114953B2 (en) |
| EP (1) | EP1987072B1 (en) |
| CN (1) | CN101389674A (en) |
| AU (1) | AU2007217731A1 (en) |
| BR (1) | BRPI0708180A2 (en) |
| CA (1) | CA2646415A1 (en) |
| DE (1) | DE102006027760A1 (en) |
| RU (1) | RU2008134182A (en) |
| WO (1) | WO2007096200A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103336006A (en) * | 2013-07-10 | 2013-10-02 | 圣象实业（江苏）有限公司 | Method used for detecting resin curing degree of sticky membrane paper laminated woodwork surfaces |
| CN106370774A (en) * | 2016-08-23 | 2017-02-01 | 濮阳绿宇泡绵有限公司 | Improved chemical method for analyzing structure of melamine resin |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SI2197927T1 (en) | 2007-10-12 | 2018-01-31 | Borealis Agrolinz Melamine Gmbh | Thermoplastically processible aminoplastic resin, thermoset microfibre non-wovens, and process and plant for their production |
| EP2743282B1 (en) | 2012-12-11 | 2020-04-29 | Borealis Agrolinz Melamine GmbH | Melamine-aldehyde-condensation product and method obtaining the same |
| DE102015014525A1 (en) | 2015-11-11 | 2017-05-11 | Giesecke & Devrient Gmbh | Security pigment based on core-shell particles and method of making same |
| FR3044058B1 (en) | 2015-11-25 | 2017-12-22 | Valeo Materiaux De Friction | FRICTION FITTING COMPRISING AN ETHERIFIED MELAMINE RESIN |
| CN105949416B (en) * | 2016-06-16 | 2019-01-18 | 浙江农林大学 | A kind of quarternary copolymerized melamine-impregnated resin glue and preparation method thereof |
| CN105906772B (en) * | 2016-06-16 | 2019-01-18 | 浙江农林大学 | A kind of melamine-formaldehyde resin adhesive and its interior modeling method preparation process |
| CN105985502B (en) * | 2016-06-16 | 2018-07-17 | 浙江农林大学 | A kind of low-temperature setting melamine-formaldehyde resin adhesive and preparation method thereof |
| ES2938660T3 (en) | 2016-10-11 | 2023-04-13 | Ostthueringische Mat Fuer Textil Und Kunststoffe Mbh | Low Emission Melamine Formaldehyde Nonwovens and Felts |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE905850C (en) | 1938-07-12 | 1954-03-08 | Cassella Farbwerke Mainkur Ag | Process for the preparation of N-substitution products of melamine |
| US2980637A (en) * | 1957-12-04 | 1961-04-18 | Monsanto Chemicals | Coating compositions containing aminoplast resins |
| US3056755A (en) * | 1957-12-04 | 1962-10-02 | Monsanto Chemicals | Protective coating compositions comprising a ternary mixture of an oilmodified alkyd resin and an etherified formaldehyde resin |
| DE1103582B (en) * | 1959-10-23 | 1961-03-30 | Henkel & Cie Gmbh | Process for the production of curable aminotriazine condensation products |
| DE19515277A1 (en) | 1995-04-26 | 1996-10-31 | Basf Ag | Process for the production of continuous fibers from melamine / formaldehyde condensation products |
| US5916999A (en) * | 1996-04-22 | 1999-06-29 | Basf Aktiengesellschaft | Process for producing filaments from melamine/formaldehyde condensation products |
| GB0116249D0 (en) | 2001-07-05 | 2001-08-29 | Imp College Innovations Ltd | Methods |
| ES2292832T3 (en) | 2001-11-19 | 2008-03-16 | Ami Agrolinz Melamine International Gmbh | PRODUCTS, ESPECIALLY POLYMER MOLDING MASSES CONTAINING TRIAZINE SEGMENTS, PROCEDURE FOR MANUFACTURING AND USES. |
| AR040209A1 (en) * | 2002-06-14 | 2005-03-16 | Agrolinz Melamin Gmbh | RESIN AMINO MOLDING MATERIAL FOR PRODUCTS WITH IMPROVED FLEXIBILITY AND RESIN AMINO PRODUCTS WITH IMPROVED FLEXIBILITY |
| DE10251653A1 (en) | 2002-10-31 | 2004-07-15 | Ami Agrolinz Melamine International Gmbh | Aminotriazine copolymers with improved water solubility, their use and process for their preparation |
| US20050014869A1 (en) * | 2003-07-18 | 2005-01-20 | Brogan John C. | Curable compositions of N-alkyl melamine formaldehyde and carbamate resins |
| DE10333892A1 (en) | 2003-07-22 | 2005-02-10 | Ami-Agrolinz Melamine International Gmbh | Plastic product of high strength and flexibility |
| US20050282994A1 (en) * | 2004-06-18 | 2005-12-22 | Brogan John C | N-alkyl melamine formaldehyde crosslinking and curable compositions |
-
2006
- 2006-06-09 DE DE102006027760A patent/DE102006027760A1/en not_active Withdrawn
-
2007
- 2007-02-22 EP EP07711705.9A patent/EP1987072B1/en not_active Not-in-force
- 2007-02-22 CN CNA2007800062472A patent/CN101389674A/en active Pending
- 2007-02-22 AU AU2007217731A patent/AU2007217731A1/en not_active Abandoned
- 2007-02-22 BR BRPI0708180-4A patent/BRPI0708180A2/en not_active Application Discontinuation
- 2007-02-22 CA CA002646415A patent/CA2646415A1/en not_active Abandoned
- 2007-02-22 US US12/280,246 patent/US8114953B2/en active Active
- 2007-02-22 RU RU2008134182/04A patent/RU2008134182A/en not_active Application Discontinuation
- 2007-02-22 WO PCT/EP2007/001692 patent/WO2007096200A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103336006A (en) * | 2013-07-10 | 2013-10-02 | 圣象实业（江苏）有限公司 | Method used for detecting resin curing degree of sticky membrane paper laminated woodwork surfaces |
| CN106370774A (en) * | 2016-08-23 | 2017-02-01 | 濮阳绿宇泡绵有限公司 | Improved chemical method for analyzing structure of melamine resin |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2008134182A (en) | 2010-03-27 |
| EP1987072A1 (en) | 2008-11-05 |
| US20090054616A1 (en) | 2009-02-26 |
| DE102006027760A1 (en) | 2007-08-30 |
| EP1987072B1 (en) | 2017-09-13 |
| WO2007096200A1 (en) | 2007-08-30 |
| BRPI0708180A2 (en) | 2011-05-17 |
| AU2007217731A1 (en) | 2007-08-30 |
| US8114953B2 (en) | 2012-02-14 |
| CA2646415A1 (en) | 2007-08-30 |
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Open date: 20090318 |